CN104560177B - Heavy hydrocarbon oil hydro-conversion method - Google Patents
Heavy hydrocarbon oil hydro-conversion method Download PDFInfo
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- CN104560177B CN104560177B CN201310523079.1A CN201310523079A CN104560177B CN 104560177 B CN104560177 B CN 104560177B CN 201310523079 A CN201310523079 A CN 201310523079A CN 104560177 B CN104560177 B CN 104560177B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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Abstract
The invention provides a heavy hydrocarbon oil hydro-conversion method. The method comprises the following steps that: (1) heavy oil enters a first reactor in the presence of hydrogen and in the presence or absence of a hydrogen-thermal cracking catalyst to be subjected to a hydrogen-thermal cracking reaction under a thermal cracking condition; (2) the reaction product in the first reactor is separated into light distillate, heavy distillate and residual oil; (3) the residual oil, the hydrogen-thermal cracking catalyst and hydrogen enter a second reactor to be subjected to a hydrogen-thermal cracking reaction at a relatively low temperature; (4) the reaction product in the second reactor is separated into light distillate, heavy distillate and residual oil; and (5) the heavy distillate enters a fixed-bed hydrotreating reactor, contacts with an aromatic hydrogenation catalyst and is subjected to a hydrogenation saturation reaction under an aromatic hydrogenation condition, and the hydrogenated heavy distillate is recycled to the first reactor; and the reacting temperature of the second reactor is 5-50 DEG C lower than that of the first reactor. Compared with the prior art, the method has the advantages of remarkably improving the heavy oil conversion rate and light oil yield, and improving the light rate of heavy distillate.
Description
Technical field
The present invention relates to a kind of heavy hydrocarbon oil raw material modifies group technology, more precisely one kind will face hydrogen thermal cracking,
Distillation and the integrated method to convert heavy charge of fixed bed hydrogenation process.
Background technology
With the continuous change weight of crude oil extraction, market, light-weight fuel oil demand is continuously increased and environmental requirement increasingly
Improve, each refinery increasingly pays close attention to residual oil weight-lightening technology.Residual oil weight-lightening method has hot-working and catalysis processing two big class.
Cn101463267a patent discloses one kind using visbreaking come processing heavy oil, realizes the side of heavy oil lighting
Method, the method be visbreaking raw material is first carried out vacuum distillation obtain heavy distillate and > 540 DEG C of decompression residuum, then followed again
Ring oil first carry out visbreaking then by its with > 540 DEG C of decompression residuum mix in Fractionator Bottom, mixed material carries out visbreaking again and splits
Change.The method can improve visbreaking conversion ratio, improve viscosity and the stability of visbreaking residue, but heavy oil lightweight conversion ratio is relatively
Low, only 10～30%.Patent cn101724450a disclose a kind of hydrogen supply agent and residual oil mixing after in pressure 15～40mpa, temperature
The coprocessing method for modifying of 0.2～5 hour under the conditions of 300～500 DEG C of degree, in the method, hydrogen supply dissolvent can be to coking in heavy oil
The cracking reaction of precursor provides hydrogen, prevents its coking；Inferior raw material can be processed, and coking yield is relatively low.
Hot-working has the advantages that adaptability to raw material is strong, but its residual oil cracking conversion ratio is low, and yield of light oil is low.Catalysis adds
Work utilizes catalyst degradation cracking reaction activation energy, improves cracking reaction speed, improves residual oil cracking conversion ratio and light oil is received
Rate.Cn101993723a discloses a kind of modifying low-quality heavy oil method and apparatus, and it relies on catalytic cracking unit, arranges inferior heavy
Oily reforming reactor, forms the modifying low-quality heavy oil technique of fluidisation state, this technique by the use of carbon deposit reclaimable catalyst as heat carrier
Cherry P process yield of light oil can be improved, but it is only suitable for the two of the inferior heavy oil raw material of low heavy metal (ni+v) content
Secondary processing.Us5300212 discloses a kind of inferior heavy oil hydrogenation modifying process method, and the method is heavy oil feedstock, hydrogen and urges
Agent is realized converting in two reactors, and concrete grammar is raw oil and molybdenum phosphate is advanced for the disperse type catalyzer of precursor
Enter first slurry bed system hydrogenation reactor, carry out conversion reaction, product under the conditions of 343～482 DEG C, 50～5000psi
Separated after enter second boiling bed hydrogenation reactor, 343～399 DEG C, 800～4000psi, loaded catalyst effect
Under converted, product enters distillation column, obtains<524 DEG C fractions and>524 DEG C of fractions, wherein<524 DEG C of fractions are as product
Product, > 524 DEG C of heavy distillat loop back second reactor.This process can achieve the modification of inferior heavy oil, but the method first
Individual reactor adopts disperse type catalyzer, and second reactor adopts loaded catalyst, the catalysis that first reactor is taken out of
Agent granule easily blocks the duct of second reactor heavy-load catalyst or the active center of covering catalyst, causes catalysis
The inactivation of agent, the operation cycle of impact whole process.
Heavy oil architecture, composition extremely complex, its different structure unit, different component lighting path and needs anti-
Answer condition different, for being easier to conversion component such as the component containing chain alkyl, cyclic alkyl structure, cracking reaction only occurs
Realize lighting；And for aromatic ring structure, especially condensed-nuclei aromatics then needs aromatic ring elder generation saturation recracking just can realize aromatic ring
The minimizing of number, the lighting of condensed-nuclei aromatics.Therefore, if reacted under identical reaction conditions, inevitable difficult to reach is relatively
Good modification effect.
Content of the invention
The technical problem to be solved in the present invention is different for heavy oil various component conversion property, on the basis of prior art
On, provide a kind of heavy oil using double-reaction area to face hydrogen method for thermal cracking, to improve heavy oil conversion ratio and lightweight rate.
A kind of heavy hydrocarbon oil hydrogenating conversion process, there is hydrogen in (1), presence or absence of the bar facing hydrogen hot cracking catalyst
Under part, heavy oil enters first reactor, carries out facing hydrogen heat cracking reaction under cracking conditions；(2) first reactor is anti-
Product is answered to be separated into light distillate, heavy distillate and residual oil；(3) residual oil with face hydrogen hot cracking catalyst, hydrogen enter second anti-
Answer device, carry out at a lower temperature facing hydrogen heat cracking reaction；(4) second reactor product separates and obtains light distillate, weight
Distillate and residual oil；(5) described heavy distillate enters fixed bed hydrotreating reactors, contacts with aromatic hydrocarbon hydrogenation catalyst,
Carry out under aromatics hydrogenation conditions being hydrogenated with saturated reaction, the heavy distillate after hydrogenation loops back first reactor；Wherein second reaction
The reaction temperature of device is lower than the reaction temperature of first reactor 5～50 DEG C.
In the method that the present invention provides, the high 2～13mpa of pressure ratio first reactor of preferred second reactor.
The present invention provide method in, described first reactor reaction condition is: reaction temperature be 400～480 DEG C, excellent
Select 420～460 DEG C, reaction pressure is 0.1～20mpa, preferably 5～12mpa, volume space velocity is 0.5～3.0h-1, preferably 0.7～
2h-1, hydrogen counterweight oil volume is than for 0～3000nm3/m3, preferably 300～1500nm3/m3, catalyst charge is 0～10000
μ g/g, preferably 100～2000 μ g/g；Described second reactor reaction condition is: reaction temperature is 380～440 DEG C, preferably
400～430 DEG C, reaction pressure is 11～30mpa, preferably 12～25mpa, and volume space velocity is 0.1～2.0h-1, preferably 0.2～
0.8h-1, hydrogen is 500～4000nm to residual oil volume ratio3/m3, preferably 800～2000nm3/m3, catalyst charge is 1000
～50000 μ g/g, preferably 2000～30000 μ g/g；The operating condition of described fixed bed hydrotreating reactors is: reaction temperature
Spend for 350～420 DEG C, reaction pressure is 6～30mpa, air speed is 0.1～5h-1, hydrogen to oil volume ratio be 400～2000nm3/m3.
In the method that the present invention provides, the described hydrogen hot cracking catalyst that faces is: containing metal constituent element and nonmetallic constituent element,
On the basis of the gross weight of catalyst, this catalyst contains the metallic element of 2-15 weight % and the nonmetallic unit of 85-98 weight %
Element, wherein, on the basis of the weight of metallic element, described metallic elements more than 95 weight % is v, ni and lanthanide series metal unit
Element and/or b race metallic element；On the basis of the weight of nonmetalloid, described nonmetalloids more than 95 weight % is
C and s, also contains a small amount of h and n, and at least partly described s and described metallic element are deposited with the sulphided form of this metallic element
?.
Compared with prior art, the having the beneficial effect that of method that the present invention provides
The method that the present invention provides will be faced hydrogen thermal cracking unit, separative element and fixed bed hydrogenation processing unit and be combined and be used for
Convert heavy oils into as light ends oil, flexible operation.Facing hydrogen thermal cracking unit using two different reactions of reaction severity
Device, first reactor is realized easily converting the conversion of component in heavy oil, and second reactor is realized difficult conversion component in heavy oil and contained
The lighting of condensed ring aromatic ring structure component, first reactor heavy oil lightweight rate to 20～80%, first reactor unconverted
Heavy distillat enter second reactor continue reaction, by wherein strengthening differential responses, the weight of two reactors in differential responses
The total lightweight rate of oil reaches 80～100%.Significantly improve heavy oil conversion ratio and yield of light oil.Face hydrogen thermal cracking process by
After one reactor reaction product separates, heavy distillate enters second reactor, and unconverted residual oil loops back second reactor can increase by the
Two reactor heavy distillate concentration and face hydrogen hot cracking catalyst reserve, improve the lightweight rate of heavy distillate.
Brief description
The schematic flow sheet of the method for catalytic conversion of heavy oil that accompanying drawing 1 provides for the present invention.
Wherein: r1 is first reactor, hr2 is second reactor, and d1 is separation equipment, and hr3 is processed for fixed bed hydrogenation
Reactor；1 is first reactor feed line, and 4 is second reactor catalyst line, and 5 is hydrogen gas lines, and 2,3,6～15 are
Material pipeline.
Accompanying drawing 2 is the sem photo facing hydrogen hot cracking catalyst a2.
Accompanying drawing 3 is the sem photo facing hydrogen hot cracking catalyst a3.
Accompanying drawing 4 is the sem photo facing hydrogen hot cracking catalyst a5.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not intended to limit the present invention.
The heavy oil hydrogenation conversion method that the present invention provides, comprising: (1) there is hydrogen, presence or absence of facing hydrogen thermal cracking
Under conditions of catalyst, heavy oil enters first reactor, carries out facing hydrogen heat cracking reaction under cracking conditions；(2) by first
The product of reactor is separated into light distillate, heavy distillate and residual oil；(3) residual oil with face hydrogen hot cracking catalyst, hydrogen
Enter second reactor, carry out at a lower temperature facing hydrogen heat cracking reaction；(4) second reactor product separates and obtains gently
Distillate, heavy distillate and residual oil；(5) described heavy distillate enters fixed bed hydrotreating reactors, with aromatic hydrogenation catalysis
Agent contacts, and carries out being hydrogenated with saturated reaction, the heavy distillate after hydrogenation loops back first reactor under aromatics hydrogenation conditions；Wherein
The reaction temperature of second reactor is lower than the reaction temperature of first reactor 5～50 DEG C, and the pressure ratio first of second reactor is anti-
Answer the high 2～13mpa of device.
In the method that the present invention provides, described heavy oil feedstock refers to boiling range in crude oil > 500 DEG C of fraction, or density is big
In 1.0g/cm3Or metal (ni+v) content is more than the petroleum hydrocarbon oil of 200 μ g/g, raw material is selected from heavy crude, crude distillation obtains
Residue oil, catalytic cracked oil pulp, coal tar, ethylene bottom oil, shale oil, viscous crude, oil sands bitumen, fixed bed and boiling bed residual oil
The various heavier feeds producing in hydrogenation tail oil, coal liquefaction tail oil and refinery's production process.
In step (1), the operating condition of first reactor is: reaction temperature is 400～480 DEG C, preferably 420～460 DEG C,
Reaction pressure is 0.1～20mpa, preferably 5～12mpa, and volume space velocity is 0.5～3.0h-1, preferably 0.7～2.0h-1, hydrogen pair
Fresh feed volume ratio is 0～3000, preferably 300～1500.
Can add in step (1) or be added without facing hydrogen hot cracking catalyst, preferably add and face hydrogen hot cracking catalyst, urge
Agent addition is 0～10000 μ g/g, preferably 100～2000 μ g/g.The described hydrogen hot cracking catalyst that faces consists of containing 2-
C, s of v, ni of 15 weight % and lanthanide element and/or b race metal and 85-98 weight % and a small amount of h and n, and
S therein and metallic element are existed with the sulphided form of this metallic element, the described average grain facing hydrogen hot cracking catalyst
Footpath is 0.01～200 micron, preferably 1～50 micron.The described microstructure facing hydrogen hot cracking catalyst is preferably lamella heap
Long-pending body, minimum unit body lamella length dimension is 40nm～50nm, thickness 1nm～20nm.
Step (1) carries out pretreatment to heavy oil feedstock, realizes the lighting of easy Cracking Component in heavy oil system.Step (1)
Heavy oil lightweight rate is controlled to be 20～80%, preferably 30～70%, further preferably 40～60%.Described lightweight rate refers in raw material >
500 DEG C of fractions be converted into < mass yield of 500 DEG C of fractions, computing formula is=(500 DEG C in 1- product+500 DEG C of yield/raw material+
Content) × 100.According to the corresponding relation between feedstock property and reaction condition, (reaction temperature, stopped by adjusting reaction condition
Stay the time) to control heavy oil lightweight rate, for example, can improve the lightweight rate of heavy oil in raising reaction temperature and the time of staying.
In the method that the present invention provides, step (2) is that the product to the first reaction zone carries out separating, can be high for heat
Point, low point of heat, cold high score, cold low point, flash distillation, air-distillation, the combination of one or more separate modes such as vacuum distillation, mainly
It is that the product of step (1) is divided into light distillate, heavy distillate and residual oil, wherein said double distilled is divided into boiling point, and < 500 DEG C evaporate
Point, preferably boiling point < 480 DEG C of fractions.
In the method that the present invention provides, step (3), in second reactor, in hydrogen, faces the presence of hydrogen hot cracking catalyst
In lower heavy oil, the condensed-nuclei aromatics of more difficult conversion is hydrogenated with lighting further, and the operating condition of second reactor is: reaction temperature is
380～440 DEG C, preferably 400～430 DEG C, reaction pressure be 11～30mpa, preferably 12～25mpa, volume space velocity be 0.1～
2.0h-1, preferably 0.2～0.8h-1, hydrogen is 500～4000, preferably 800～2000 to fresh feed volume ratio.Second reaction
Area's reaction temperature is lower than the first reaction zone 5～50 DEG C, the high 2～13mpa of pressure of the pressure ratio first reactor of second reactor.
Add in second reactor and face hydrogen hot cracking catalyst, the described hydrogen hot cracking catalyst that faces can be with the first reaction
In device to face hydrogen hot cracking catalyst identical or different.Described faces the addition of hydrogen hot cracking catalyst with respect to the second reaction
Residual oil raw material in device is 1000～50000 μ g/g, preferably 2000～30000 μ g/g.
Step (4) separates the product of second reactor, can be hot high score, low point of heat, cold high score, cold low point, sudden strain of a muscle
The combination of one or more separate modes such as steaming, air-distillation, vacuum distillation, mainly by step (3) to face hydrogen thermal cracking anti-
Answer product to be divided into light distillate, heavy distillate and residual oil, wherein said double distilled be divided into boiling point < 500 DEG C of fractions, preferably boiling point <
480 DEG C of fractions, distillation range of residual oil is > 524 DEG C of fractions.The residual oil isolated loops back and continues reaction in second reactor.
Get rid of outside a small amount of residual oil preferably step (4) isolated, the amount getting rid of outward residual oil is 0～6wt% of total residual oil；Remaining
Residual oil loops back and continues reaction in second reactor.
Step (5) is to introduce fixed bed hydrogenation process reaction by separating the heavy distillate obtaining in step (2) and step (4)
In device, carry out aromatic hydrogenation saturated reaction, load hydrocatalyst for saturating arylhydrocarbon in fixed bed reactors, described is hydrocracked
Catalyst is made up of the active metal component of load regulation vib race and/or viii race on heat-resistant inorganic oxide.Preferably aoxidize
Ni and/or mo is loaded on alumina supporter, more preferably on alumina support, loads the catalyst of ni and mo.The behaviour of hydrocracking reactor
It is: reaction temperature is 350～420 DEG C that reaction pressure is 6～30mpa as condition, volume space velocity is 0.1～5.0h-1, hydrogen oil body
Long-pending ratio is 400～2000nm3/m3.
In the method that the present invention provides, the described product of first reactor separates and can be total to the product of second reactor
With a set of separation equipment it is also possible to be respectively adopted different separation equipments.Preferably share same set of separation equipment.When using same
During set separation equipment, isolate light distillate, heavy distillate and residual oil, get rid of outside residual fraction, remaining residual oil introduces the second reaction
Device carries out facing hydrogen heat cracking reaction at a lower temperature；Heavy distillate enters fixed bed reactors and carries out hydrocracking reaction.Its
In, the boiling range of light fraction is initial boiling point～200 DEG C, and the boiling range of described heavy distillat is 200 DEG C～500 DEG C, and described residual oil is
Boiling point > 500 DEG C of fraction.
When using different separation equipment, in step (2), first reactor product is separated into light distillate, heavy distillate
And residual oil, the boiling range of wherein light distillate is: initial boiling point～200 DEG C, and the boiling range of heavy distillate is 200～420 DEG C, the evaporating of residual oil
Journey is boiling point > 420 DEG C of fraction.In step (4), second reactor product is separated into light distillate, heavy distillate and residual oil, its
The boiling range of middle light fraction is initial boiling point～200 DEG C, and the boiling range of described heavy distillat is 200 DEG C～524 DEG C, and described residual oil is boiling
Point > 524 DEG C of fraction.
In the method that the present invention provides, preferably two are faced hydrogen thermal cracking reactor and share a set of separation equipment, can realize
Reduce investment outlay on the premise of separation function.
The wherein said hydrogen hot cracking catalyst that faces faces hydrogen modifying catalyst for a kind of heavy oil, and the gross weight with catalyst is
Benchmark, this catalyst contains the metallic element of 2-15 weight % and the nonmetalloid of 85-98 weight %, wherein, with metallic element
Weight on the basis of, more than 95 weight % described metallic element is v, ni and lanthanide element and/or b race metal
Element；On the basis of the weight of nonmetalloid, described nonmetalloids more than 95 weight % is c and s, and at least part of institute
State s to exist with the sulphided form of this metallic element with described metallic element.Described b race metallic element can be any
B race metallic element, as at least one in cr, mo and w it is preferable that described b race metallic element is mo and/or w,
Described lanthanide series metal is preferably at least one in la, ce, pr and nd.
In the method that the present invention provides, the described hydrogen hot cracking catalyst composition that faces is preferably mo-ni-v-la, mo-ni-
v-ce、mo-ni-v、w-ni-v-ce.On the basis of the gross weight of catalyst, in described catalyst, the content of v is 0.1-5.0 weight
The content of amount %, ni is 0.05-4.0 weight %, and the content of lanthanide element is 0-5.0 weight %, b race metallic element
Content is 0-15.0 weight %, and the total content of lanthanide element and b race metallic element is 1-20 weight %.
The described mean diameter facing hydrogen hot cracking catalyst is 0.01～200 micron, preferably 1～50 micron.More preferably
The microgranular microstructure facing hydrogen hot cracking catalyst be preferably lamella packed structures, described lamella length dimension is received for 40
Rice～50 nanometers, 1 nanometer～20 nanometers of thickness.Face hydrogen hot cracking catalyst using preferably employing sheet catalyst particle,
Have that catalyst loading is few, heavy oil high conversion rate, the effect of distillate high income.
In the method that the present invention provides, the described preparation method facing hydrogen hot cracking catalyst includes: by source metal and non-
Source metal in the presence of solvent and under the conditions of vulcanization reaction with sulfurizing agent, obtain facing hydrogen hot cracking catalyst.Wherein, institute
Stating source metal is the material containing v, ni and lanthanide element and/or b race metallic element, described non-metal source be containing
There is the material of carbon, described source metal, non-metal source contain in gained solid product after making to contact with the consumption of vulcanizing agent
The metallic element of 2-15 weight % and the nonmetalloid of 85-98 weight %, and on the basis of the weight of metallic element, 95 weight %
Above described metallic element is v, ni and lanthanide element and/or b race metallic element；Weight with nonmetalloid
On the basis of amount, described nonmetalloids more than 95 weight % is c and s.
Described source metal can provide in any suitable form, such as with the Organic substance of metallic element in this source metal and/
Or the form of inorganic matters provides it is preferable that as with the oxide of metallic element, inorganic salt, acylate and organic chelate
At least one form provides, and specifically, the inorganic salt of described metallic element can be nitrate, sulfate, hydrochlorate and carbon
At least one in hydrochlorate, or the oxysalt for this metallic element, such as tungstates, molybdate, the having of described metallic element
Machine hydrochlorate can be oleate, naphthenate and more specifically, such as molybdenum dialkyl-dithiophosphate, nickel carbonyl and six carbonyls
Vanadium etc., described organic chelate can be for example the polycomponent coordination compound of metal in source metal, its ligand include six teeth, eight
Tooth or ten tooth parts, these parts include but is not limited to following compound: edta, dtpa, edpa.
Described non-metal source can be provided in the form of any material of carbon elements, as described non-metal source can be with former
The form of at least one of oil, heavy oil, oil sands bitumen, asphalitine, white carbon black, graphite powder, coal dust, coke and activated carbon provides.
In order that source metal and non-metal source mixing is more uniform, described contact is preferably carried out under agitation, stirs
Mix speed 300～1200rpm, and the condition of described contact make to contact after in gained solid product metallic element sulfide shape
Become the granule that size is 5-50 nanometer, preferably 10-30 nanometer.
When the activated carbon that described activated carbon is through peracid treatment, the catalyst of more preferable catalytic effect can be obtained.Excellent
Selection of land, the method for described process activated carbon includes the methods such as deionized water wash, salt acid elution and nitric acid oxidation.
Being added to of described solvent makes reaction system evenly, when non-metal source is for liquid, can have concurrently simultaneously
The function of solvent, it is therefore preferred that described non-metal source can be together with solvent, jointly with crude oil, distillate, residual oil and thick
The form of at least one of oil provides.And when non-metal source is for solid-state, the addition of described solvent can also be in very wide range
Interior change, for example, described solvent can be 10-1000:1, preferably 20-200:1 with the weight ratio of metallic element in source metal,
More preferably 20-100:1
Using the conventional vulcanization reaction condition in this area with vulcanizing agent can achieve the present invention it is preferable that described vulcanizing agent
For at least one in Sublimed Sulfur, Carbon bisulfide, high-sulfur heavy oil, mercaptan and dimethyl sulfide；The condition bag of described vulcanization reaction
Include, temperature is 250-400 DEG C, pressure is 5.0-10.0mpa, the time is 15-480 minute, stir speed (S.S.) 300～1200rpm；Enter
One step is preferably, and the condition of described vulcanization reaction includes, and temperature is 300-380 DEG C, and pressure is 6.0-8.0mpa, and the time is 30-
240 minutes, most preferably 60-240 minute, stir speed (S.S.) 500～1000rpm.Wherein, described pressure is hydrogen first pressing.This preparation
Raw material can be prepared in method and need to be aged 0～36h, preferably 1～24h.
Under preferable case, also include removing in reacted product in the described preparation method facing hydrogen hot cracking catalyst
Solvent, e.g., when described solvent be water when, preferably reacted product is filtered.When described solvent is solvent naphtha, this
The method of invention preferably also includes with toluene, reacted product being stripped, and the purpose of extracting is to remove solvent naphtha therein
And partly unreacted Organic substance in non-metal source.
In the method that the present invention provides, the preparation side facing hydrogen hot cracking catalyst that described microstructure is piled up for lamella
Method is: the organo-metallic compound containing metal ni, v, vi race and lanthanide series metal is dissolved in organic solvent, is subsequently adding sulfuration
Agent, flowable carbonaceous material, and 600rpm～1000rpm rotating speed stir 10min～30min, be aged 12～16 hours, so
After be rapidly heated and carry out vulcanization reaction to curing temperature, conditions of vulcanization is reaction temperature is 350-360 DEG C, and pressure is 6.0-
8.0mpa, the time is 60-80 minute.
Below in conjunction with the accompanying drawings 1, the method that present invention offer is provided, but the present invention is not therefore subject to any limit
System.
The schematic flow sheet of the mink cell focus catalysis conversion method that Fig. 1 provides for the present invention, as shown in figure 1, heavy oil or heavy oil
Enter first reactor r1 with after the hydrogen premix of pipeline 1 through first reactor feed line 2, there is hydrogen, adding
Or reacted under conditions of being added without facing hydrogen hot cracking catalyst, realize easily converting component in first reactor r1 in heavy oil
Lighting；The product of first reactor enters separation equipment d1 through pipeline 3, pipeline 8 and is separated into light distillate, heavy distillat
Oil and residual oil；Wherein, light distillate removes reaction system through pipeline 9 as product.Residual oil is through pipeline 10 discharging, a small amount of residual oil warp
Get rid of outside pipeline 13, remaining residual oil is mixed with the hydrogen facing hydrogen hot cracking catalyst, being derived from pipeline 5 from pipeline 4 through pipeline 12
Uniformly enter second reactor hr2 through pipeline 6, carry out facing hydrogen heat cracking reaction in second reactor hr2, realize heavy oil more difficult
The conversion component i.e. lighting containing condensed ring aromatic ring structure component；The product of second reactor hr2 is entered through pipeline 7, pipeline 8
Enter and in separation equipment d1, be separated into light distillate, heavy distillate and residual oil.From separation equipment d1 heavy distillate through pipeline 11
Enter fixed bed hydrotreating reactors hr3, depositing in the case of hydrogen, contact with hydrocracking catalyst and carry out hydrogenation and split
Change reaction, hydrocracking reaction product, through pipeline 14 discharging, loops back and continues reaction in first reactor r1.
The method illustrating present invention offer below by embodiment, but the present invention is not therefore subject to any limit
System.
In embodiment and comparative example, the heavy oil feedstock of employing takes from Tahe oil plant, and its property is shown in Table 1.Can from table 1
See, heavy oil feedstock density is big, and hydrogen-to-carbon ratio is low, and carbon residue is up to 25.9wt%, and asphalt content is up to 21wt%, tenor
Height, belongs to the reluctant inferior raw material of generally conventional method for modifying.
The hydrogen hot cracking catalyst that faces in embodiment adopts following methods to prepare:
In autoclave, by 5.89g ammonium molybdate ((nh4)6mo7o24·4h2O), 7.40g nickel nitrate (ni (no3)2·
6h2O), 1.78g vanadium oxide (v2o5), 4.8g Lanthanum (III) nitrate (la (no3)3·6h2O), mix with 300ml water, be stirring evenly and then adding into
81.2g priority is the vulcanizing agent (Sublimed Sulfur) of the hydrochloric acid of 2mol/l and the activated carbon of nitric acid treatment and 7.8g through over-richness,
Under 300rpm rotating speed stir 30min, be aged 8h, then in 300 DEG C, 7.0mpa(hydrogen first pressing), the bar of high-speed stirred (300rpm)
Vulcanize 120min, product obtains catalyst a1 after filtering, being dried, and the elementary composition analysis of catalyst a1 is listed in table 1 under part.?
Electric Microscopic observation, the mean diameter of catalyst a1 is 10 μm, and the mean diameter of metallic element sulfide is 15nm.
By 43.7g molybdenum naphthenate (mo accounts for 10.3 weight %), 30.8g aphthenic acids tungsten (w accounts for 8.78 weight %), 6.2g tetra- carbonyl
Nickel (ni accounts for 33.73 weight %), 6.5g Vanadium hexacarbonyl. (v accounts for 23.29 weight %), 25.3g isooctoate of rare earth metal (la accounts for 4.8 weight %,
Ce accounts for 7.1 weight %), the residual oil (Kuwait's decompression residuum) of 17.7g vulcanizing agent (dmds) and 295ml sequentially add the height of 500ml
Pressure kettle in, under 800rpm rotating speed stir 30min, be aged 14h, then stir in 370 DEG C, 6.0mpa(hydrogen first pressing), high-speed stirring
Mix and vulcanize 60min under conditions of (800rpm), product is centrifuged, toluene extract, be vacuum dried and obtain catalyst a2, be catalyzed
The elementary composition of agent a2 is listed in table 1.In electric Microscopic observation, the mean diameter of catalyst a2 is 5 μm, metallic element sulfide flat
All particle diameter is 40nm, and the a2 catalyst pattern of sem photo display simultaneously is lamellar structure, and lamellar structure length is 60～100nm, thick
Spend for 2～10nm.
By 5.7g molybdenum dialkyldithiocarbamacompositions (mo content 8.7%), 3.6g nickel octoate, 2.9g aphthenic acids vanadium, 2.8g
Aphthenic acids praseodymium, 100ml recycle oil, 5.6g vulcanizing agent (Sublimed Sulfur) and 88g crude oil are added sequentially in 500ml autoclave,
Stir 45min under 1000rpm rotating speed, be aged 16h, then in 350 DEG C, 8.0mpa(hydrogen first pressing), high-speed stirred (1000rpm)
Under the conditions of vulcanize 80min, product through filter, vacuum drying after obtain catalyst a3, the elementary composition of catalyst a3 is listed in table 1.
In electric Microscopic observation, the mean diameter of catalyst a3 is 0.5 μm, and the mean diameter of metallic element sulfide is 10nm, sem photo
Display a3 catalyst pattern is lamellar structure, and lamellar structure length is 40～50nm, and thickness is 2～10nm.
By 30.4g molybdenum dialkyl-dithiophosphate (mo accounts for 5.7 weight %), (ni accounts for 33.73 weights to 30.4g nickel carbonyl
Amount %), 6.5g Vanadium hexacarbonyl. (v accounts for 23.29 weight %), 28.2g cerium naphthenate (ce accounts for 8.6 weight %), 4.9g vulcanizing agent (distillation
Sulfur), the solvent naphtha (hydrogenated diesel oil) of 200ml and 57.2g heavy oil asphalt matter (Qing Chuan 3# bitumen, c content 88.9%, h content
7.2%, s content 5.8%, n content 1.1%) it is added sequentially in the autoclave of 500ml, stir 20min, ageing under 300rpm rotating speed
4h, then in 350 DEG C, 8.0mpa(hydrogen first pressing), vulcanize 210min under conditions of high-speed stirred (500rpm), product is through centrifugation point
Obtain catalyst a4 from the extracting of, toluene, vacuum drying, the elementary composition of catalyst a4 is listed in table 1.In electric Microscopic observation, it is catalyzed
The mean diameter of agent a4 is 1 μm, and the mean diameter of metallic element sulfide is 12nm.
By 30.4g aphthenic acids tungsten (w accounts for 8.78 weight %), 30.4g nickel carbonyl (ni accounts for 33.73 weight %), 6.5g six carbonyl
Base vanadium (v accounts for 23.29 weight %), 28.2g cerium naphthenate (ce accounts for 8.6 weight %), 4.9g vulcanizing agent (Sublimed Sulfur), 200ml return
Oil refining and 57.2g petroleum coke, are added sequentially in the autoclave of 500ml, stir 20min under 500rpm rotating speed, are aged 2h, then
In 350 DEG C, 8.0mpa(hydrogen first pressing), vulcanize 210min under conditions of high-speed stirred (500rpm), product is centrifuged, toluene
Extracting, vacuum drying obtain catalyst a5, and the elementary composition of catalyst a5 is listed in table 1.Sem observes catalyst a5, and pattern is in micro-
Spherical, mean diameter is 1 μm, and tem analysis result shows that the mean diameter of metallic element sulfide is 50nm.Wherein, catalyst
Accompanying drawing is shown in by the sem photo of a2, a3 and a5.
Face hydrogen hot cracking catalyst composition and be shown in Table 2.Wherein, in catalyst the content of various elements by x-ray fluorescence spectrum
Method records, and measures the valence state of element by x-ray power spectrum, judges the existence form of metallic element in catalyst according to result；
The mean diameter of the mean diameter of catalyst and sulfide is passed through high-resolution scanning nuclear microprobe analysis and is obtained.
The hydrocatalyst for saturating arylhydrocarbon that hydroprocessing processes use is that the rn-400(aluminium oxide of standard catalyst company is born
The ni-mo catalyst carrying).
Embodiment 1-7 illustrates the lighting effect of the method for catalytic conversion of heavy oil that the present invention provides.
Embodiment 1
Using device flow process as shown in Figure 1, heavy oil feedstock, by being pumped into preheating furnace, enters first anti-after preheating
Device is answered to be reacted, the product of first reactor enters separation equipment d1 and is separated into light distillate, heavy distillate and residual oil,
Light distillate removes response system, and heavy distillate goes follow-up fixed bed hydrotreating reactors hr3, residual oil with face hydrogen thermal cracking
Catalyst a1, hydrogen enter second reactor and carry out facing hydrogen heat cracking reaction, and the product of second reactor enters to separate and sets
Standby d1, isolates light distillate, heavy distillate and residual oil, remaining residual oil loops back second reactor；Heavy distillate and hydrogen enter
Enter fixed bed reactors hr3, contact with hydrocatalyst for saturating arylhydrocarbon rn-400, the heavy distillate after aromatic hydrogenation saturated reaction
Loop back first reactor.Plant running post-sampling analysis in 4 hours measures toluene insolubles content and boiling range in product, root
According to the cracking rate of<500 DEG C of fraction oil yields calculate in heavy oil feedstock>500 DEG C of residual oil in product simulation distillation, toluene insoluble
Thing yield is defined as process coking yield.Operating condition is shown in Table 3, and reaction result is listed in table 4.Coke forming property generates first in oil to measure
Benzene insoluble content is weighing.
Embodiment 2
Using device and flow process with embodiment 1, except that separation equipment d1 separates getting rid of outside the residual fraction obtaining,
Remaining residual oil faces hydrogen heat cracking reaction with facing in hydrogen hot cracking catalyst a2 entrance second reactor, and operating condition is shown in Table 3, reaction
Result is listed in table 4.
Embodiment 3
Using device and flow process with embodiment 2, except that heavy oil feedstock, hydrogen and face hydrogen hot cracking catalyst a1
Enter first reactor after preheated to carry out facing hydrogen heat cracking reaction.Operating condition is shown in Table 3, and reaction result is listed in table 4.
Embodiment 4
Using device and flow process with embodiment 3, except that from the residual oil of separation equipment d1 and facing hydrogen thermal cracking
Catalyst a3 enters in second reactor and faces hydrogen heat cracking reaction, and operating condition is shown in Table 3, and reaction result is listed in table 4.
Embodiment 5
Using device and flow process with embodiment 3, except that the hydrogen hot cracking catalyst that faces in first reactor is
A2, the hydrogen hot cracking catalyst that faces in second reactor is a5.Operating condition is shown in Table 3, and reaction result is listed in table 4.
Embodiment 6
Using device and flow process with embodiment 4, except that heavy oil feedstock, hydrogen and face hydrogen hot cracking catalyst a2
Enter first reactor after preheated to carry out facing hydrogen heat cracking reaction.Operating condition is shown in Table 3, and reaction result is listed in table 4.
Embodiment 7
Using device and flow process with embodiment 5, except that from the residual oil of separation equipment d1 and facing hydrogen thermal cracking
Catalyst a4 enters in second reactor and faces hydrogen heat cracking reaction.Operating condition is shown in Table 3, and reaction result is listed in table 4.
Comparative example 1-4 illustrates the effect of heavy oil lightening method in prior art.
Catalyst b preparation method: by 10g iron naphthenate (fe content 12%), it is former that 4g vulcanizing agent (Sublimed Sulfur) is added to heavy oil
In material, directly it is warming up to reaction temperature, iron naphthenate decomposes in temperature-rise period, vulcanizes, online generation catalyst b, catalyst b
Consist of fe-20%, s-22.8%, c-57.2%.In electric Microscopic observation, catalyst b is spherical in shape, and mean diameter is 30～50 μm,
The mean diameter of iron sulfide is～1 μm.
Comparative example 1-2
Using batch reactor, heavy oil feedstock is entered together with hydrogen batch reactor and reacted, reaction is produced
The separated equipment of thing is divided into gas, liquid and solid, and product liquid obtains<500 DEG C of distillates and>500 through gas chromatographic analysiss
DEG C unconverted heavy oil yield, calculates toluene insolubles yield according to solid product amount, judges the green coke trend of product.Reaction
Condition and reaction result are listed in table 5.
Comparative example 3-4
Using batch reactor, disperse type catalyzer b.By heavy oil feedstock and iron naphthenate (fe content 12%), vulcanizing agent
(Sublimed Sulfur), hydrogen enter batch reactor together and are reacted, and the separated equipment of product is divided into gas, liquid and consolidates
Body, product liquid obtains<500 DEG C of distillates and>500 DEG C of unconverted heavy oil yields through gas chromatographic analysiss.Reaction condition and anti-
Result should be listed in table 5.
From table 3-5, data can be seen that and faces hydrogen thermal cracking using the double-reaction area of the present invention and hydrotreating combines
Method, part residual oil loop back second reactor, heavy distillate hydrogenation Posterior circle return first reactor, increased the second reaction
Device catalyst inventory, substantially increases heavy oil conversion ratio and fraction oil yield, and embodiment 1,2 is that residual oil raw material is first thermally treated to be made
Easily conversion ratio 25%～40% is realized in the conversion of conversion component, then converts further in second reactor, finally realizes 500 DEG C of products of ＜
Thing yield>70%,>500 DEG C of slag oil cracking conversion ratios>65%, toluene insolubles yield<0.5%；Compare the pure thermal transition of comparative example 1
Reaction, 500 DEG C of product yields of ＜ improve 10 percentage points, > 500 DEG C of slag oil cracking conversion ratios improve 11 percentage points, first
Benzene insoluble yield declines 33 percentage points.
Embodiment 3 compares comparative example 2, and 500 DEG C of product yields of ＜ improve 14 percentage points, > 500 DEG C of slag oil cracking conversion ratios
Improve 16 percentage points, toluene insolubles yield declines 10 percentage points.
Comparative example 3,4 is that residual oil has carried out slurry bed system hydrogenation reaction under a kind of oil-soluble mo catalyst precursor acts on
As a result, 500 DEG C of product yields<69% of its ＜,>500 DEG C of slag oil cracking conversion ratios<65%, toluene insolubles yield>5%；And this
500 DEG C of product yields of ＜ in bright embodiment of the method 4～7 > 80%, > 500 DEG C of slag oil cracking conversion ratios > 82%, toluene insolubles yield
< 2%, effect is superior to comparative example 3,4.
Table 1 heavy oil feedstock property
| Project | Numerical value |
| Density (20 DEG C)/(g cm-3) | 1.0378 |
| W (carbon residue)/% | 25.9 |
| W (element)/% | |
| c | 85.64 |
| h | 10.00 |
| s | 3.1 |
| n | 0.6 |
| W (four components)/% | |
| Saturation is divided | 15.8 |
| Fragrance point | 37.1 |
| Colloid | 25.7 |
| Asphalitine | 21.4 |
| W (metal)/(μ g g-1) | |
| ca | 19.1 |
| fe | 18.3 |
| ni | 58 |
| v | 395 |
| Simulation distillation boiling range/DEG C | |
| Initial boiling point | 393 |
| 5% | 457 |
| 10% | 486 |
Table 2 catalyst composition data
Table 3
In table, catalyst concn is all in terms of metal.
Table 4 embodiment experimental result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| First reactor | |||||||
| 500 DEG C of product yield/% of ＜ | 37.00 | 41.61 | 51.93 | 58.77 | 61.77 | 63.95 | 65.93 |
| > 500 DEG C of slag oil cracking rate/% | 28.41 | 33.65 | 45.38 | 53.15 | 56.56 | 59.03 | 61.28 |
| Toluene insolubles/% | 0 | 0 | 0 | 0 | 0.06 | 0.13 | 0.41 |
| Double-reactor | |||||||
| 500 DEG C of product yield/% of ＜ | 69.75 | 73.45 | 79.48 | 82.26 | 84.81 | 87.83 | 89.49 |
| > 500 DEG C of slag oil cracking rate/% | 65.63 | 69.83 | 76.68 | 79.84 | 82.74 | 86.17 | 88.06 |
| Toluene insolubles/% | 0.40 | 0.50 | 0.76 | 0.84 | 0.98 | 1.18 | 1.62 |
Table 5 comparative example experimental result
Claims (13)
1. a kind of heavy hydrocarbon oil hydrogenating conversion process is it is characterised in that comprise the following steps:
(1) there is hydrogen, presence or absence of under conditions of facing hydrogen hot cracking catalyst, heavy oil enters first reactor, in heat
Carry out under cracking conditions facing hydrogen heat cracking reaction；(2) product of first reactor is separated into light distillate, heavy distillate
And residual oil；(3) residual oil with face hydrogen hot cracking catalyst, hydrogen enter second reactor, carry out at a lower temperature facing hydrogen hot tearing
Change reaction；(4) second reactor product separates and obtains light distillate, heavy distillate and residual oil；(5) described heavy distillate enters
Enter fixed bed hydrotreating reactors, contact with aromatic hydrocarbon hydrogenation catalyst, carry out being hydrogenated with saturated reaction under aromatics hydrogenation conditions,
Heavy distillate after hydrogenation loops back first reactor；Wherein second reactor reaction temperature than first reactor reaction temperature
Spend low 5～50 DEG C；The described hydrogen hot cracking catalyst that faces contains metal constituent element and nonmetallic constituent element, and the gross weight with catalyst is
Benchmark, this catalyst contains the metallic element of 2-15 weight % and the nonmetalloid of 85-98 weight %, wherein, with metal unit
On the basis of the weight of element, described metallic elements more than 95 weight % is v, ni and lanthanide element and/or b race gold
Belong to element；On the basis of the weight of nonmetalloid, described nonmetalloids more than 95 weight % is c and s, also contains a small amount of
H and n, and at least partly described s and described metallic element are existed with the sulphided form of this metallic element.
2. according to claim 1 method it is characterised in that described second reactor pressure ratio first reactor pressure
High 2～13mpa.
3. according to claim 1 or 2 method it is characterised in that described first reactor operating condition is: reaction temperature is
400～480 DEG C, reaction pressure is 0.1～20mpa, and volume space velocity is 0.5～3.0h-1, hydrogen is 0 to heavy oil volume feed
～3000nm3/m3, facing hydrogen hot cracking catalyst addition is 0～10000 μ g/g；Described second reactor reaction condition is:
Reaction temperature is 380～440 DEG C, and reaction pressure is 11～30mpa, and volume space velocity is 0.1～2.0h-1, hydrogen is to residual oil raw material
Volume ratio is 500～4000nm3/m3, facing hydrogen hot cracking catalyst addition is 1000～50000 μ g/g；Described fixed bed adds
The operating condition of hydrogen treatment reactor is: reaction temperature is 350～420 DEG C, and reaction pressure is 6～30mpa, and volume space velocity is
0.1～5h-1, hydrogen to oil volume ratio be 400～2000nm3/m3.
4. according to claim 3 method it is characterised in that described first reactor operating condition is: reaction temperature be 420
～460 DEG C, reaction pressure is 5～12mpa, and volume space velocity is 0.7～2h-1, hydrogen to heavy oil volume feed be 300～
1500nm3/m3, facing hydrogen hot cracking catalyst addition is 100～2000 μ g/g；Described second reactor operating condition is: anti-
Temperature is answered to be 400～430 DEG C, reaction pressure is 12～25mpa, volume space velocity is 0.2～0.8h-1, hydrogen is to residual oil raw material body
Long-pending ratio is 800～2000nm3/m3, facing hydrogen hot cracking catalyst addition is 2000～30000 μ g/g.
5. according to claim 1 method it is characterised in that the described mean diameter facing hydrogen hot cracking catalyst be 0.01～
200 microns.
6. according to claim 5 method it is characterised in that the described mean diameter facing hydrogen hot cracking catalyst is 1～50
Micron.
7. according to claim 5 or 6 method it is characterised in that the described microstructure facing hydrogen hot cracking catalyst is piece
Rotating fields, its length dimension is 40nm～50nm, thickness 1nm～20nm.
8. according to claim 1 or 2 method it is characterised in that in described step (2) and step (4) adopt same set of point
From equipment, the product from step (1) and step (3) is separated into light distillate, heavy distillate and residual oil.
9. according to claim 8 method it is characterised in that the boiling range of described light distillate is initial boiling point～200 DEG C, described
The boiling range of heavy distillat be 200 DEG C～500 DEG C, described residual oil is boiling point > 500 DEG C of fraction.
10. according to claim 1 or 2 method it is characterised in that described hydrocatalyst for saturating arylhydrocarbon is heat resistant inorganic oxygen
Load regulation viii race metal component in compound.
11. according to claim 1 or 2 method it is characterised in that described hydrocatalyst for saturating arylhydrocarbon is heat resistant inorganic oxygen
Load vib race and viii race metal component in compound.
12. according to claim 1 or 2 method it is characterised in that described heavy oil feedstock refers to boiling range in crude oil > 500 DEG C
Fraction, or density is more than 1.0g/cm3Or the content of metal ni and metal v is more than the petroleum hydrocarbon oil of 200 μ g/g.
13. according to claim 12 method it is characterised in that described heavy oil is to obtain selected from heavy crude, crude distillation
Residue oil, catalytic cracked oil pulp, coal tar, ethylene bottom oil, shale oil, viscous crude, oil sands bitumen, fixed bed and boiling bed residual oil
Hydrogenation tail oil, coal liquefaction tail oil.
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